Carboxylic acid amide monoazo dyestuffs



United States Patent CARBOXYLIC ACID AMIDE MONOAZO DYESTUFFS Karl Ronco, Riehen, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Apr. 6, 1964, Ser. No. 357,782 Claims priority, application Switzerland, May 14, 1962, 5,768/ 62 7 Claims. (Cl. 260-204) This application is a continuation-in-part of my copending application Ser. No. 279,633, filed May 10, 1963, and now abandoned.

The present invention provides valuable new carboxylic acid amide azo dyestuffs free from groups imparting solubility in Water, especially sulphonic acid and carboxylic acid groups, which correspond to the general formula in which X represents a member selected from the group consisting of halogen, nitro, trifluoromethyl, carbalkoxy and cyano, Y represents a member selected from the group consisting of hydrogen, halogen and trifluoromethyl, Z and Z represent members selected from the group consisting of hydrogen and halogen atoms, X is a member selected from the group consisting of hydrogen, methyl, methoxy and halogen, X is a member selected from the group consisting of hydrogen, chlorine and niethoxy, Y and Y represent members selected from the group consisting of hydrogen, methoxy, methyl, and chlorine Z Z and Z represent members selected from the group consisting of hydrogen, halogen, methyl, lower alkoxy, lower carbalkoxy and phenyl.

The new dyestulfs are obtained when (a) a halide of a mono-carboxylic acid of the formula OH R2 OOOH free from acidic groups imparting solubility in water is condensed in a molar ratio of 1:1 with an amine of the formula 0 ONHR3CO OH free from acidic groups imparting solubility in Water is condensed in a molar ratio of 1:1 with an amine of the formula 3,329,671 Patented July 4, 1967 in which formulae the residues R to R have the meanings given above.

The azo-carboxylic acids of the Formula 3 are obtained by coupling a diazo compound of an aromaticv monoamine free from acidic groups imparting solubility in water, especially an aminobenzene, with a Z-hydroxy- 3-naphthoic acid. The following amines may be mentioned as diazo bases:

4-amin0-3-nitrotrifluoromethylbenzene, 5-amino-2-nitrotrifluoromethylbenzene, 3-amino-4-nitrotrifiuoromethylbenzene, 4-chloro-2-nitro-l-aminobenzene, 3-aminotrifluoromethylbenzene, 5chloro-2-aminobenzoic acid methyl ester, anthranilic acid methyl ester,

2 4 5 -trichloro-1 -aminobenzene,

The azo-carboxylic acids of the Formula 5 are obtained either by coupling a diazo compound of one of the above-mentioned aromatic monoamines with a carboxylic acid of the formula 0 ONH-R C OOH in which R and R have the meanings given above, or by condensing a halide of a mono-carboxylic acid of the Formula 3 with an amino earboxylic acid of the formula H NR -COOH The azo-carboxylic acids obtained are treated with agents capable of converting carboxylic acids into their acid halides, for example, their acid chlorides or bromides, such agents being more especially phosphorus halides, for example, phosphorus penta-bromide, phosphorus trichloroide or phosphorus pentachloride, phosphorus oxyhalides or advantageously thionyl chloride. The treatment with such acid halogenating agents is advantageously carried out in an inert organic solvent, for example, dimethyl formamide, a chlorobenzene, for

example, monoor di-chlorobenzene, toluene, xylene or nitrobenzene. If desired the last five named solvents can be used in the presence of dimethyl formamide.

In the manufacture of the carboxylic acid halides it is generally of advantage first of all to dry the azo compounds, which are prepared in aqueous medium, or to free them from water by azeotropic distillation with an organic solvent. If desired, this can be carried out immediately before the treatment with the acid hologenating agents.

In method (a) of the present invention the monocarboxylic acid chlorides obtained as described above are condensed in a molar ratio of 1:1 with aromatic monoamines of the Formula 4. As example the following amines may be mentioned:

114-dichloro-2-benzoylamino-5-(4-chloro-3 '-arnino benzylaminobenzene,

1 z4-dichloro-2-benzoylamino-5 (2 4-dichloro-5 -.amino) benzoylaminobenzene,

1 :4-dichloro-2-benzoylamino-S- (3 '-arnino -benzoylaminobenzene,

1 :4-dichloro-2-benzoylamino-5 4-methoXy-3 -amino) benzoylaminobenzene, :4-dimethyl-Z-benzoylarnino-5 (3 -amino) benzoylaminobenzene, 1 :4-dimethyl-2-benzoylamino-5 (4'-chloro-3 '-amino-) benzoylaminobenzene, 1 :4-dimethyl-2-benzoylamino-5 (4-methoxy-3 -amino) benzoylaminobenzene, 1-chloro-4-methoxy-2-benzoylamino-5- (4'-methox-y-3 amino) -benzoylaminobenzene, 1-chloro-4-methoxy-2-benzoylamino-5- (4'-chloro-3 amino) -benzoyla-minobenzene, 1methyl-4-chloro-2-benzoylarnino-5- (4-methoxy-3 amino) -benzoylaminobenzene, l-methyl-4-chloro-2-benzoylamino-5- (4'-chloro-3 amino) -benz-oy1aminobenzene, 1-chloro-4-methoxy-2-benzoylamino-5- (3 '-amino benzoylaminobenzene, 1-methyl-4-chloro-2-benzoylamino-5- (3 '-amino benzoylaminobenzene, lz4-dimethyl-2-benzoylamino-S- (2 :4-dichloro-5 tamino) -benzoylaminobenzene, :4-dichloro-2 4-chl-oro -benzoylamino-5 (4-chloro- 3 "-amino) -benzoylaminobenzene, :4-dichloro-2 (4-chloro -benzoylamino-5 (2" 4"-dichloro-S "-amino -benzoylaminobenzene, :4-dichloro-2 4'-chloro) -benzoylamino-5 (4-chloro- 3 "-amino) -benzoylaminobenzene, 1:4-dichloro-2(2' :4'-dichloro -benzoylamino-5- (2 :4-

dichloro-S "-amino) -benzoylaminobenzene, :4-dichloro-2: u-naphthoylamino-5(2 4-dichloro-5'- amino) -benzoylaminobenzene and :4-dichloro-2 (2' 4-dichloro -benzoylamino-5 (3 amino) -benzoylaminobenzene.

The condensation of the above described carboxylic acid halides with the amines is advantageously carried out in .an anhydrous medium. Under these conditions the condensation generally takes place surprisingly quickly at temperatures within the boiling range of the common organic solvents, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, and the like. In order to accelerate the reaction, it is generally of advantage to add an agent capable of binding acid, for example, anhydrous sodium acetate or pyridin. Some of the dyestuffs obtained are crystalline and some are amorphous and they are generally obtained in a good yield and in a pure form. It is of advantage first to separate the acid halides but in some cases this may be dispensed with without trouble, and the condensation carried out immediately following the formation of the carboxylic acid halide.

The new dyestuifs are valuable pigments which can be used for a very wide variety of purposes. They are generally obtained in such a form that special processing is not required. They are particularly suitable for the spin-dyeing of rayon, viscose, cellulose ethers or esters, polyamides, polyurethanes or polyesters. They may also be used for the manufacture of coloured lacquers or lake formes, in which application they are distinguished by a good fastness to overstripe bleeding, and for the colouration of solutions or products of cellulOse acetate, nitrocellulose, natural or synthetic resins, for example polymerization or condensation resins, such as aminoplasts, .alkyl resins, phenoplasts, polyolefines such as polystyrene, polyvinylchloride, polyethylene, polypropylene, poly acrylonitrile, rubber, casein, silicone and silicone resins. They can also advantageously be used in the manufacture of coloured pencils, cosmetic preparations or laminated sheet material.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by Weight:

Example 1 122 parts of the dyestufr", obtained by diazotising 4-trifluoromethyl-2-nitro-l-aminobenzene in glacial acetic acid or with nitrosyl sulphuric acid and coupling with 2:3- hydr-oxynaphthoic acid, were heated, while stirring, for 1 hour at to C. with a mixture of 1000 parts of ortho-dichlorobenzene, 5 parts of dimethylformamide and 50 parts of thionyl chloride. After cooling the reaction mixture, the homogeneously crystalline mono-carboxylic acid chloride of the dyestuff so obtained was isolated by filtration, washed with .a small amount of cold orthodichlorobenzene and benzene, and then dried in vacuo at 55 to 60 C.

17 parts of this acid chloride were added to 800 parts of cold ortho-dichlorobenzene while stirring. A warm solution of 18 parts of 1:4-dichloro-2-benzoylamino-5(4- chloro-3-amino)-benzoylaminobenzene in 400 parts of ortho-dichlorobenzene were then added and the mixture stirred for 12 hours at to C. After the condensation, the pigment, consisting of small bent needles, was filtered while hot, washed successively with hot orthodichlorobenzene, hot benzene, methanol and water and then dried in vacuo at 70 to 80 C. The condensation product of the formula ITIOQ No. I II III IV 52 4-trifluorornethyl-2-nitro-1- 1:4-dichloro-2-benzoylamino-5-(3-amino-4- Orange.

aminob enz ene. methyl) -benzoylaminoh enzene.

53 .do l-chloro-4-methyl-2-benzoylamino-5 (3-amino- Yellow-orange.

4J-methoxy) -b enzo ylaminob enz ene.

54 "do 1z4-din1ethoxy-2-benzoylamino-5-(3-arnin0-4- Red-orange.

moth ox y) -benz oylarninoh enzene.

55 .do 1 4-dicl1loro-2-(4-phenyl)-benzoylan1in0-5-(3- D0.

amino-4 -ehlro) -b enz oylaminobenzene.

56 do 1z4-diol1loro-2-( Y-methyl)-benzoylan1ino-5(4"- Yellow-orange.

cl1loro-3 -ainino) -benzoylaminobenzene.

57 do 1:4-dichloro-2:a-naphthOylamino-S-(2:4- Orange.

dichloro--amino) -b enz oyl-aminob enzene.

58 .do 1:4-dichloro-2-benzoylamino-5-(5-amino- 1 Do.

111Gti1OXY2 Cl1l0l'O)-b enzoylaminobenzene.

59 .do 1:4-diehloro-2-(4-cl1loro)-benzoylamino-5-(5"- D o.

arnino-4-methoxy-2-el1loro) -benzoylaminobenzene.

60 do l-benzoylamino-4-( t ehloro-ii amino)-benzoyl- D o.

ami nob enzene.

61 do 1,4-dichloro-2-benz0ylamino-5-(5-amino-2,4- D o.

dimethoxy) -benzoylarninobenzene.

62 do 1,4-diehloro-2-(3,4-dich1oro)-benzoylamin0-5- Yellow orange.

(4 -chl0ro-3 -arnino) -benzovlaminobenzene.

63 .do 1,4-diehr0-2-(4-carbomethoxy)-benz0ylamino- Orange.

5- 1 -chloro-3 -metl10xy) -benzoylamino 1) enz ene.

64 .do 1,4-dimethyl-2-(4-brornobenzoylarnino-5-(4- Do.

ehloro-3 -amino) -benzoylaminob enzene.

65 1,4-dichloro-2-(2-fiuoro)-benz0ylamino-5'(4"- Do.

1neth0xy-3-amino) -beuzoylaminobenzene.

66 I10 1,4-diohloro-2(4-phenyl)-benzoylarnino-5-(5- D0.

amino-2 ,4-dichloro)-henzoylarninobenzene.

67 J10 1,4-dichloro-2-(4-phonyl)-benzoylamin0-5-(4- Do.

chloi'o-S -ainino) -benzoylaminob enzene.

68 J10 1,4-dichloro-2-(4 methyl) -benzoylan1ino-5-(4 Do.

chloro-S '-amino) -10 enzoylaminob enzene.

69 l,4-dimethyl-2-(3-methyl)-benzoylamino-5-(4- Do.

chloro 3 -arnino -benzo ylaminobenzene.

70. "J o 1,4-dichloro-2-(2-n1ethyl)-benzoylamino-5- (4- D0.

methoxy-3-a;mino)-benzoylaminobenzene.

71 J10 1,4-di0hlor0-2-(2-meth0Xy)-benzoyla.mino5-(4- Do.

chlor0 3-a1nino) -b enzoylaminobenz ene.

73.. 1,-dichloro-Z-benzoylarnino-5-(4-bromo-3- D0.

amino) -b enzoylamino.

74- 1,4-dich1oro-2-benzoylamino-5(4 -fluoro-3 Do.

amino) -b enzoylaminob enzene 75 1-benzoylamino-4-(3-aminobenzoyl)-amino- Do.

b enzoyl.

Example 2 The pigment dyestuff of the formula 15.4 parts of the mono-azo dyestufr obtained by coupling diazotized 5-chloro-2-aminobenzoic acid methyl ester with 2:3-hydroxy-naphthoic acid, were heated in a finely divided form for 1 hour at 115 to 120 C. with a mixture of 200 parts of ortho-dichlorobenzene, 5 parts of thionyl chloride and 1 part of dimethylformamide while stirring. After cooling a crystalline mono-carboxylic acid chloride was isolated by filtration, washed with benzene, and then dried in vacuo at 50 to 60 C.

6.05 parts of this acid chloride were introduced into 100 parts of ortho-dichlorobenzene, while stirring, at 100 C. A hot solution of 3.1 parts of 5-amino-4-methoxy-2- chlorobenzoic acid in 50 parts of ortho-dichlorobenzene was then added and the mixture stirred for hours at 140 to 145 C. The condensation product was filtered at 100 C., washed with hot orthodichlorobenzene and benzene and then dried in vacuo at 60 to 70 C. .7.1 parts of the aid condensation product, in a finely divided state, were heated for 2 hours at 115 to 120 C. in admixture with 100 parts of orthodichlorobenzene, 2 parts of thionyl chloride and 0.3 part of dimethylformamide while stirring. After cooling the reaction mixture, the mono-carboxylic acid chloride was isolated by filtration, washed with ortho-dichlorobenzene and benzene, and then dried in vacuo at 50 to 60 C. 1.17 parts of this acid chloride were introduced into 100 parts of ortho-dichlorobenzene at 100 C. while stirring. A hot solution of 0.6 part of 2:5 dichloro-4-benzoylamino 1 aminobenzene in parts of ortho-dichlorobenzene was then added and the mixture stirred for 14 hours at 140 to 145 C. The pigrnent thus formed was filtered at 120 C., washed successively with hot ortho-dichlorobenzene, benzene and methanol and water and then dried in vacuo at to C.

III 01 N or OH oONH-Q-NHGOO CONH o1 OCH;

was an orange powder very sparingly soluble in organic solvents and when in a fine state of division, coloured polyvinyl chloride foils orange tints possessing a very good fastness to migration and to light.

By using 5-methyl-4-benzoylamino-2 chloro-1-aminobenzene or 5-chloro-4-benzoylamino-2-methoxy-l-aminobenzene or 2:5-dichloro-4:u-naphthoylamino l aminobenzene for the condensation instead of 2:5-dichloro-4- benzoylamino-aniline, pigments possessing similar properties were obtained.

Example 3 16.5 parts of the mono-azo dyestuif obtained by coupling diazotized 4-.amino-3-nitrobenzotrifluoride with 2- hydroxy-3-naphthoic acid-*(2'-chloro-5-carboxy)-phenylamide were heated for one hour at to C. with a mixture of 300' parts of ortho-dichlorobenzene, 4 parts of thionyl chloride and 0.5 part of dimethylformamide while stirring. After cooling, the monocarboxylic acid chloride was filtered, washed with benzene and then dried in vacuo at 50 to 60 C.

1.15 par-ts of this mono-ca-r-boxylic acid chloride were introduced into 80 parts of cold ortho-dichlorobenzene while stirring. 9.6 parts of 2:5-dichloro-4-benzoy1amino .and then dried in vacuo at 70 to 80 C. A soft-grained,

e 9 4 10 l-aminobenzene in 20 parts of oithodichlorobenzene were in which Z represents a member selected from the group then added, and the whole heated for 16 hours at 140 to consisting of hydrogen and bromine atoms, X is a mem- 14s c. The pigment, which precipitated in crystalline ber selected from the group consisting of hydrogen, form, was then filtered at 120 0, washed with hot methyl, methoxy and chlorine, 3 is member selected ortho-dichlorobenzene, benzene, methanol and water, 5 from the group sti g of hydrogen, chlorine and methoxy, Y and Y represent members selected from the group consisting of hydrogen, methoxy, methyl and chlorine, Z Z and Z represent members selected from the group consisting of hydrogen, chlorine, methyl, lower same structural formula as that given in Example 1. i fg gjg g:g g g g gi gi gqgg ijfg f:

By using 2:5-dichloro-4-(4'-ch1oro)-benzoyl-.aminoani- Benzene g line instead of 2:S-dichloro-4-benzoylamino-aniline, a The dyestufl of the formula pigment possessing similar properties was obtained.

orange powder Was obtained which coloured poly-vinyl chloride foil yellow-orange tints possessing an excellent fastness to light and to migration. The product had the IITOz Example 4 '65 parts of stabilized polyvinyl chloride, 35 parts of L} dioctyl phthalate and 0.2 part of the dyestulf obtained as described in the second paragraph of Example 1 were 01 mixed together and worked to and from on a two-roll calender for 7 minutes at 140 C. A yellow-orange foil CONH C1 possessing a very good fastness to light and to migration was obtained. CONH -NHCO- What is claimed is: 1. An azo dyestulf of the formula 22 o oNHOXa Y:

Z4 a Z5 in which Z represents a member selected from the 4. The dyestulf of the formula group consisting of hydrogen and bromine atoms, X NO:

is a member selected from the group consisting of hydrogen, methyl, methoxy and chlorine, X is a member se- O lected from the group consisting of hydrogen, chlorine Q and methoxy, Y and Y represent members selected from the group consisting of hydrogen, methoxy, methyl OH 01 and chlorine, Z Z and Z represent members selected from the group consisting of hydrogen, chlorine, methyl, CONE C1 01 lower alkoxy lower carbalkoxy and phenyl groups, and

wherein the residue Z and Z together, can also form CONH NHCOQ a fiused benzene ring. I

2. An azo dyestufi of the formula 1 Zg- C ONH X3 Y3 a ONH NHCOQ 1 1 1 2 5. The dyestuff of the formula 7. The dyestuff of the formula ll 5 II N N -OH :1 -c ONE-O01 01 -c ONH- 01 I 10 I 0 ONE NHCO- 01 CONE-ONHCOO I 6. The dyestuif of the formula 15 References Cited 1 UNITED STATES PATENTS o 1,947,550 2/1934 Hitch T 260-204 u 3,124,568 3/1964 Mory et a1. 260204 X 20 CHARLES B. PARKER, Primary Examiner.

FLOYD D. HIGEL, Assistant Examiner.

OH (I31 C ONE-Q01 C1 Cl C ONH NHCOOC1 

1. AN AZO DYESTUFF OF THE FORMULA 